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Preparation and characterization of copper oxide thin films deposited by filtered cathodic
vacuum arc
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Abstract
Copper oxide thin films deposited on Si (100) by a filtered cathodic vacuum
arc with and without substrate bias have been studied by atomic force
microscopy, x-ray diffraction (XRD), x-ray photoelectron spectroscopy
(XPS) and Raman spectroscopy. The results show that the substrate bias
significantly affects the surface morphology, crystalline phases and texture.
In the film deposited without bias, two phases—cupric oxide (CuO) and
cuprous oxide (Cu2 O)—coexist as cross-evidenced by XRD, XPS and
Raman analyses, whereas CuO is dominant concurrent with CuO (020)
texture in the film deposited with bias. The film deposited with bias exhibits
a more uniform and clearer surface morphology although both kinds of films
are very smooth. Some explanations are given as well.
2. Experimental details
82
Preparation and characterization of copper oxide films
300 450
Cu2O
sample A 400 Cu2O sample A
250 CuO Cu O sample B CuO (111) (200) sample B
2
(-111) (111) 350 (-111)
(002) (002) CuO
(111)
Intensity (a. u.)
200 300
Cu2O (200)
Intensity
(200) 250
150 CuO CuO
(111) (020) 200 CuO
CuO (200) (202) CuO (020)
100 (110) 150 (110)
100
50
50
0 0
30 35 40 45 50 55 60 30 35 40 45 50 55 60
2θ (°) 2θ (°)
Figure 2. Glancing angle XRD patterns of samples A and B. It is Figure 3. Normal mode XRD patterns of samples A and B to
seen that cupric and cuprous oxides coexist in sample A, whereas characterize the texture of the samples. It is again observed that
sample B is composed of the pure CuO phase. CuO and Cu2 O coexist in sample A while CuO exists in sample B,
consistent with the glancing angle XRD results.
The other two weak peaks at 38.3˚ and 55.4˚ hardly change
in intensity. No obvious peak shift can be observed. It is
1600
interesting to note that all peaks are associated with CuO crystal CuO
planes for sample B, showing that the thin film deposited with sample A Cu2O
bias voltage is a pure monoclinic CuO phase or that the fraction 1400
sample B
of crystalline Cu2 O is so small that it cannot be detected. This
indicates the substrate bias can noticeably affect the phase 1200
Si
Intensity
0.9λ
D= , Figure 4. Raman spectra of samples A and B, agreeing well with the
B cos θ
XRD results for sample composition identification. The broadening
where λ is the x-ray wavelength, θ is the Bragg diffraction of the Cu2 O profile in sample B may be attributed to the amorphous
angle, and B is the full-width at half-maximum (FWHM) of characteristic of the phase which could not be detected by XRD.
the peak corresponding to θ. When calculated by using the
peak corresponding to the (002) plane of CuO, the resultant exists in sample B, consistent with the glancing angle XRD
grain sizes are 9.3 nm and 5.4 nm, respectively, for samples A results.
and B. Note that the FWHM of the peak is obtained by fitting Raman spectra of samples A and B are displayed in
the XRD patterns and using the Grams/32 software, which is a figure 4. For sample A, three peaks located at around 300,
commercial software for a Renishaw Ramascope Spectrometer 340, 600 cm−1 are observed. Both the strong peak at 300 cm−1
(RENISHAW, Gloucestershire, UK). and the weak peak at 340 cm−1 are ascribed to CuO [18]. The
The textures of samples A and B are characterized by broad peak centred at 600 cm−1 is believed to be contributed by
normal mode XRD spectra. As shown in figure 3, there several Cu2 O-related sub-peaks such as 570, 618 or 624 cm−1
are four strong peaks, corresponding to the CuO (−111) and [18, 19]. In contrast, for sample B, the CuO-related peaks at
(002), Cu2 O (111), CuO (111) and (200), and Cu2 O (200) 300 and 340 cm−1 both become stronger. However, the broad
planes, and the weak peak belonging to CuO (110) plane in peak at 600 cm−1 associated with Cu2 O is largely suppressed
sample A. However, for sample B, the peak corresponding to in intensity. It is well-known that the intensity of Raman
the CuO (020) plane is prominent while other peaks are greatly scattering is directly proportional to the number of scattering
suppressed, denoting that CuO (020) preferential orientation centres present in the volume illuminated by the laser beam.
occurs. From the normal mode XRD spectra, it is again Thus, it is concluded that both CuO and Cu2 O exist in sample A
observed that CuO and Cu2 O coexist in sample A while CuO while CuO is dominant in sample B, agreeing with the result
83
Z H Gan et al
of XRD. We also note that the Cu2 O-related Raman peak does a lower binding energy of about 932.4 eV [20]. In addition
not disappear completely for sample B whereas the Cu2 O to the main peaks of Cu 2p3/2 , their satellite peaks are also
diffraction peak cannot be observed. This difference may observed at higher binding energies. This satellite feature
exist because Cu2 O does not crystallize or the amount of observed in both samples is an indication of materials having a
crystalline Cu2 O is low so that it cannot be detected by XRD. partially filled d9 shell configuration in the ground state, such
Another possible explanation is that Raman scattering is more as copper dihalides, metallic nickel, or CuO [20]. For Cu2 O
sensitive to copper oxide compared with XRD, as reported by with a completely filled shell (d10 ), this satellite peak is absent
Gong et al [18]. because screening via a charge transfer into the d states is not
A possible reason for the different phases of copper oxide allowed. Moreover, in both samples, the main peaks of 2p1/2
in the films with and without bias, could be that applying are located at a binding energy that is 20 eV higher than that
substrate bias during deposition induces impact-stimulated of their 2p3/2 main peaks. The similarity of the Cu2p XPS
chemical composition variation in the resulting films. The spectra of samples A and B proves that these surfaces are both
application of bias may lead to more incorporation of oxygen dominated by CuO. However, as concluded from the XRD
into the films as in ion beam assisted deposition. In sample A analysis, Cu2 O exists in sample A. This difference is due to
without substrate bias, CuO and Cu2 O form simultaneously. the fact that XPS, unlike XRD, can only get the composition
However, by biasing the substrate, the extra-incorporated information from surface rather than bulk. It is, therefore,
oxygen with higher energy is supposed to lead to the formation concluded that CuO and Cu2 O coexist in sample A in which
of CuO from Cu2 O, as indicated by the following reaction: CuO is dominant on its surface, whereas only CuO is present
in sample B. This assumption is supported by the Raman
Cu2 O + O → 2CuO. scattering analysis discussed earlier. Balamurugan et al [7]
also reported that Cu2 O nanoparticles were capped with a
As a consequence, the amount of Cu2 O in sample B is greatly surface layer of CuO, which stabilizes the more symmetric
reduced and almost undetectable by XRD as presented earlier. cuprous oxide phase.
As a result, the crystalline phase changes with substrate bias There are two components (one main peak S1 and one
correspondingly. satellite S2 ) in the O 1s spectra after curve decomposition is
The survey spectra of XPS for both samples A and B are performed for both samples A and B, as shown in figure 6(b).
presented in figure 5. The spectra are globally similar to each The main peaks for both cases are located at 529.8 eV. The
other. The peaks corresponding to Cu 3d, 3p, 3s, 2p and Auger, FWHM of the main peak of sample A is about 1.0 eV, which
O 1s and Auger are obviously observed. C 1s peak is also is slightly narrower than that of sample B (1.22 eV). Note
found, which is due to the exposure of the samples to air. No that both the FWHM are larger than that of single crystal
argon is seen, indicating that no argon exists in the samples cupric oxide (0.8 eV), where the satellite component almost
or the argon content is lower than the detection limit. The disappears [21]. The energy of the satellites in samples A
high-resolution spectra corresponding to Cu 2p and O 1s are and B are centred at approximately 1.6 eV and 2 eV higher
given in figures 6(a) and (b). They are plotted after correction than their main peaks, respectively. The area ratios of S1 /S2
of charging effects using a binding energy of 284.8 eV as the for samples A and B are about 1.41 and 0.65, respectively,
C 1s peak. meaning that sample B presents a larger satellite component. It
Figure 6(a) shows Cu 2p3/2 and 2p1/2 spectra. The is well-known that the main peak and satellites of O 1s spectra
respective main peaks of Cu 2p3/2 for samples A and B lie correspond to different chemical states of the oxygen atoms
at 933.7 and 933.8 eV. These main peaks can be assigned to [22]. The main peak at lower binding energy is attributed to
Cu2+ ions, rather than Cu+ ions, which have a main peak at the normal O2− , interacting with the copper atoms to form the
chemical Cu–O bond. The satellite is ascribed to the extra-
lattice oxygen [21], indicating non-stoichiometric nature of
20000 sample A O Auger the thin films. This result fits well with the differential FWHM
sample B of the main peaks between our oxide thin films and the single
Cu 2p
crystal cupric oxide. Again, the more extra-lattice oxygen in
15000
Cu Auger
sample B, i.e. a lower S1 /S2 ratio, is attributed to the higher
Intensity (a.u.)
84
Preparation and characterization of copper oxide films
(a) (b)
Figure 6. (a) Cu 2p and (b) O 1s XPS spectra of samples A and B, showing that the surfaces are both dominated by CuO. Note that the
Cu2 O phase in sample A as detected by XRD is covered by the surface CuO layer, which was also reported by Balamurugan et al [7]. The
difference between XPS and XRD is that XPS, unlike XRD, can only get the composition information from the surface rather than the bulk.
significantly affects the surface morphology, crystalline phases [9] Xu J F, Ji W, Shen Z X, Tang S H, Ye X R, Jia D Z and
and texture. In the film deposited without bias, two phases— Xin X Q 1999 J. Solid State Chem. 147 516
[10] Orel B, Svegl F, Bukovec N and Kosec M 1993 J. Non-Cryst.
cupric oxide (CuO) and cuprous oxide (Cu2 O)—coexist,
Solids 159 49
whereas CuO is dominant concurrent with the CuO (020) [11] Xu X L, Lau S P and Tay B K 2001 Thin Solid Films
texture in the film deposited with bias. Also, XRD suggests that 398–399 244
the film prepared with bias has more defects compared to the [12] Shi X, Tay B K, Tan H S, Li Z, Tu Y Q, Silva S R P and
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[13] Shi X, Tay B K and Lau S P 2000 Int. J. Mod. Phys. B 14 136
film exhibit a more uniform and clearer surface morphology.
[14] Wang X, Liu X H, Zou S C, Martin P J and Bendavid A 1996
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[17] Klug H P and Alexander L E 1974 X-Ray Diffraction
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